(Z)-vinyl chloride-d1 | 3728-37-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (Z)-vinyl chloride-d1
• 英文别名: cis-1-chloro-2-deuterio-ethene；cis-<2 d>-Vinylchlorid；cis-βd(1)-Vinylchlorid；Vinylchlorid-cis-β-d1；cis-Vinylchlorid-β-d1；cis-β-D-Vinylchlorid
• CAS: 3728-37-8
• 化学式: C₂H₃Cl
• 分子量: 63.4909
• InChiKey: BZHJMEDXRYGGRV-NYLCSIPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  3.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (Z)-vinyl chloride-d1 、 以 二氯甲烷-D2 为溶剂， 以26%的产率得到cis-[1-(2)H]Propene
  参考文献：
  名称：

  Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe⁺ Species

  摘要：

  The reaction of vinyl chloride (VC) with (alpha-diimine)PdMe+ species yields (alpha-diimine)PdCl-(propene)(+) Isotope labeling experiments using the deuterium-labeled vinyl chlorides 1-VC-d(1) and Z-VC-d(1) combined with DFT computations establish that this reaction proceeds by 2,1-insertion of VC to produce beta-H agostic (alpha-diimine)Pd(CHClCH2Me)(+), chain-walking isomerization to generate beta-Cl dative (alpha-diimine)Pd(CHMeCH2Cl)(+) and syn beta-Cl elimination. The labeling experiments rule out mechanisms involving initial 1,2-insertion or C-Cl oxidative addition. The computational results and the observation of small amounts of propene-d(2) argue against mechanisms involving 2,1-insertion followed by alpha-Cl elimination and a 1,2 H-shift.

  DOI：

  10.1021/om1000925
• 作为产物：
  描述：

  乙炔 在 双(环戊二烯)氯化锆氘化物 、 N-氯代丁二酰亚胺 作用下， 生成 (Z)-vinyl chloride-d1
  参考文献：
  名称：

  Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe⁺ Species

  摘要：

  The reaction of vinyl chloride (VC) with (alpha-diimine)PdMe+ species yields (alpha-diimine)PdCl-(propene)(+) Isotope labeling experiments using the deuterium-labeled vinyl chlorides 1-VC-d(1) and Z-VC-d(1) combined with DFT computations establish that this reaction proceeds by 2,1-insertion of VC to produce beta-H agostic (alpha-diimine)Pd(CHClCH2Me)(+), chain-walking isomerization to generate beta-Cl dative (alpha-diimine)Pd(CHMeCH2Cl)(+) and syn beta-Cl elimination. The labeling experiments rule out mechanisms involving initial 1,2-insertion or C-Cl oxidative addition. The computational results and the observation of small amounts of propene-d(2) argue against mechanisms involving 2,1-insertion followed by alpha-Cl elimination and a 1,2 H-shift.

  DOI：

  10.1021/om1000925

文献信息

• Catalytic hydrochlorination of acetylene on PdCl2/C supported catalysts: Kinetic isotopic effect of HCl/DCl, stereoselectivity, and mechanism
  作者：T. V. Krasnyakova、D. V. Nikitenko、E. V. Khomutova、S. A. Mitchenko

  DOI：10.1134/s0023158417050135

  日期：2017.9

  Two routes of catalytic hydrochlorination of acetylene were found by the isotopic label method for systems with supported palladium K2PdCl4/C and Н2PdCl4/C catalysts: with formation of the products of syn- and anti-addition of the H(D)Cl molecule to the triple bond of acetylene. Two isotopic effects that differ in magnitude were determined for these systems from the reaction kinetics and the ratio

  乙炔的催化氢氯化的两种途径是由同位素标记方法发现与所支持的钯2K体系2的PdCl 4 / C和Н 2的PdCl 4 / C催化剂：与地层的产品的顺式-和反H（D）Cl分子加成到乙炔的三键上。从反应动力学和产物的非氘代和单氘代异构体的产率比确定了这些系统的两种同位素效应，这是由于H（D）Cl分子参与了两个反应阶段：限制氯钯和快速原型金属脱金属。有效活化能和动力学同位素效应的实验误差之内一致，这表明，反应机理是类似的，该催化剂的活性中心在系统具有K 2的PdCl 4 / C和Н 2的PdCl 4 / C是相同性质。